Note: Descriptions are shown in the official language in which they were submitted.
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PROCESS OF MANUFACTURING CO-GROUND CALCIUM CARBONATE WITH
CERIA-CONTAINING ZIRCONIUM OXIDE BEADS
It is an object of the present invention to provide a process to obtain a
calcium
carbonate material comprising GCC (ground calcium carbonate) and PCC
(precipitated
calcium carbonate). Such material is appropriate for use in a number of
domains, for
example in the paper industry.
It is also an object of the present invention to provide a process to obtain a
calcium
carbonate material comprising GCC and PCC, with a specific steepness factor
(defined
as d30 / d70 x 100, where dx is the equivalent spherical diameter relative to
which x %
by weight of the particles are finer) of at least about 30, preferably of at
least about 40,
and most preferably of at least about 45. Such a material leads to superior
properties of
the paper coated with such a material, notably in terms of gloss.
It is also an object of the present invention to provide a process to obtain a
calcium
carbonate material comprising GCC and PCC, with a steepness factor of at least
about
30, preferably of at least about 40, and most preferably of at least about 45,
in a cost
efficient manner, wherein GCC and PCC are co-ground, possibly with at least
another
mineral material.
Another object of the present invention lies in the co-ground calcium
carbonate
material (i.e. : aqueous mineral slurries containing the co-ground GCC and PCC
and
dry products containing the co-ground GCC and PCC) obtained through this
process.
Another object of the present invention lies in the uses of such products in
any sector
making use of mineral materials, and notably in the paper, paint and plastic
industries.
Many types of mineral are used in the paper coating formulations for the paper
industry. Clay has traditionally been used for this purpose due to its low
cost relative to
other mineral pigments.
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Calcium carbonate (CaCO3) is used as both a coating and filling pigment, and
is
notably known to improve some of the optical properties of the final product,
such as
gloss, opacity or brightness. Calcium carbonate can be of two types: ground or
natural
calcium carbonate referred to as GCC, and synthetic or precipitated calcium
carbonate
referred to as PCC.
Ground calcium carbonate is calcium carbonate obtained from natural sources,
such as
limestone, marble or chalk, and processed through a treatment such as
grinding.
Precipitated calcium carbonate is a synthesized material, generally obtained
by
precipitation following reaction of carbon dioxide and lime in an aqueous
environment. This PCC may be rhombohedral and/or scalenohedral and/or
aragonitic.
According to the needs of the man skilled in the art, this GCC or PCC may
additionally be surface treated, for example with stearine
For many years, there has been need to supply the skilled man in the art with
mineral
slurries comprising GCC and PCC, since it may be of interest that hoth be
present in
the paper coating formulations, in order to regulate more precisely the final
properties
of the coated paper. Publications referring to the use of both natural and
precipitated
calcium carbonate in the paper industry include, for instance, "PCC or GCC,
factors
determining calcium carbonate choice in alkaline conversion" (published
following the
November 1995 28th Pulp and Paper Annual Meeting) and "GCC vs. PCC as the
primary filler for uncoated and coated wood-free paper" (Tappi Journal 2000,
83(5),
pp 76) : these publications refer to the properties of PCC/GCC blends for use
in paper
industry. In "Chalk : a calcium carbonate for the high-filled sheet" (TAPPI
Proceedings, April 5-8 1992, Papermakers Conference, Book 2, Opryland Hotel,
Nashville TNõ TAPPI Press, pp. 515-520), the author suggests that drawbacks
associated with PCC may be overcome by using this mineral in conjunction with
other
fillers, such as GCC. Finally, in "Coating structure with calcium carbonate
pigments
and its influence on paper and print gloss" (Pulp 8c Paper Canada, 2004,
105(9), pp.
43-46), the influence of different pigment blends including GCC and PCC on
paper
properties including gloss and print gloss is investigated. The Applicant
underlines that
these publications appear to belong to the technical background of the
invention, since
they attest to the need to obtain mixtures of GCC and PCC for use in paper
industry.
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However, none of these publications teach or reveal the co-grinding of both
GCC and
PCC, and the further possibility to obtain a co-ground product with a specific
steepness
factor, which is one of the objects of the present invention.
With further reference to the need of the skilled man in the art to improve
some of the
final properties of the coated paper, there is also an additional need for the
skilled man
to improve some of the optical properties of the final product, such as gloss.
Faced
with this requirement, the skilled man in the art knows that the "steepness
factor" of
the mineral material used in the paper coating formulation is a criteria of
main
importance: the selection of specific values for the steepness factor, in
relation with the
choice of a specific mineral material, can lead to an improvement in the
optical
properties of the coated paper. At this point, the Applicant indicates that a
common
way to define the steepness factor is "the ratio of the dx equivalent
spherical diameter
(at which x % by weight of the particles are finer) to the dy equivalent.
spherical
diameter (at which y % by weight of the particles are finer), multiplied by
100. In such
a way, for a given mineral material in slurry form or in the form of a dry
powder, the
steepness factor can be regarded the steepness of the corresponding
granulometric
curve.
In this area, the skilled man in the art knows WO 2003 / 089 524, which
targets a high
degree of brightness, whiteness, and fluorescence in paper coatings or filler
compositions used in cellulose based substrate and light weight coating base
paper.
The proposed solution consists of a hydrous kaolin having a GE brightness of
at least
90 and a steepness factor (d30/d70 x 100) of at least about 39. It has to be
noted that this
document does not offer teachings relating to calcium carbonate, since one of
the
requirements of the inventors is precisely to avoid the use of this mineral.
The prior art also reveals some documents dealing with the use of calcium
carbonate of
a single-type, in conjunction with specific steepness factors. EP 0 894 836
discloses a
slurry consisting of water, commercially available dispersant which prevents
the
dissociation of agglomerated pigment in the slurry, and agglomerated carbonate-
containing pigment with a particle size distribution in which 80-99 % by
weight are
below 2 pm in size, 50-90 % by weight are below 1 i.tm and 0-10 % by weight
are
below 0.2 m, a steepness factor (ratio of diameter at 50 % by weight to
diameter at 20
% by weight) is of 1.5-2.0 and a porosity is of 45-65 %. It is clearly that
this invention
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deals solely with natural calcium carbonate of the calcite, marble and chalk-
type;
moreover, the invention lies in a dispersing process and does not teach the
grinding of
the abovesaid carbonate-containing pigment. US 2002 155 055 addresses the
problem
of reducing the width of particle size distribution of calcium carbonate
compositions
for use in paper, but is exclusively focused on ground calcium carbonate, as
recognized
by the inventors (see [0007]). The proposed solution lies in a process
comprising the
step of forming a dispersant-free aqueous suspension of natural calcium
carbonate,
wet-grinding the suspension to produce a calcium carbonate composition having
steepness ratio (A) and aging the suspension at temperature below 35 C to
produce a
calcium carbonate composition having steepness ratio (B) smaller than the
ratio (A). In
this document, the steepness factor is defined as the average diameter of the
particles
in the 75 % mass divided by the average diameter of the particles in the 25 %
mass,
when the size distribution is represented using a SedigraphTM.
There are also prior art documents which deal with the use of calcium
carbonate of a
single type or of both types (GCC and PCC blends), in conjunction with at
least one
other mineral matter (and notably kaolin), and disclosing some particular
values for the
steepness factor of each material and / or of the final blend. WO 2003 / 093
577
teaches that, in order to improve gloss, opacity, brightness and smoothness of
paper,
specific particulate pigments may be useful in the paper coating formulations.
These
pigments comprise a first component, which is PCC and a second component which
is
a processed particulate hydrous kaolin clay having a shape factor of at least
25 and a
steepness of at least 20, or a first component, which is a PCC having a
spherical
particle shape and a second component which is a processed particulate hydrous
kaolin
clay having a shape factor at least 45, and a mean equivalent particle
diameter of less
than 0.5 m, or a first component which is a PCC and a second component, which
is a
processed particulate hydrous kaolin clay having a shape factor less than 25.
Moreover, WO 2002 / 016 509 teaches that to improve the optical properties of
paper
and printability of paper coatings, it is advantageous to use kaolin having a
mean
particle size of 0.7-3 um and a shape factor of at least 60; this type of
kaolin can be
used in combination with another filler such as talc, calcium sulfate and / or
alkaline
earth metal carbonate. Finally, WO 2000 / 066 510 teaches that pigment
compositions
comprising a blend of a fine kaolin produced from block kaolin clay, and a
calcium
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carbonate which may be either GCC or PCC, wherein both particles have a median
particle size less than 0.8 pm, and a steepness factor, defined as 100 x
d30/d70, greater
than 38, and wherein the kaolin / carbonate weight ratio is of 40/60,
preferably of
50/50, can improve the optical properties and printability of coated paper.
While the
5 latter three documents refer to the use of blends of calcium carbonate
(possibly of both
the GCC and pcc type), and necessarily kaolin, which is not a requirement of
the
present invention, they do not teach nor reveal the possibility to co-grind
PCC and
GCC, or even to the possibility of co-grinding kaolin with at least one type
of calcium
carbonate mineral.
Closer from the scope of the present invention, there are also documents
dealing with
the use of mixtures of GCC and PCC, notably for use in paper formulations to
enhance
some of the optical properties of the coated paper. DE 4 128 570 discloses a
carbonate
filler and pigment with specified particle shape and size for filling and
coating,paper,
giving high opacity, degree of whiteness and filler content. Such carbonate
filler and
pigment have a rhombohedral or round particle shape, a gradient factor (ratio
of
particle diameter in pm at 50 / 20 weight %) of 1.1-1.4, a ratio R of %
particles finer
than 1 pm / % particles finer than 0.6 pm ranging from 8 to 19, and average
statistic
particle diameter ranging from 0.4 to 1.5 m. Finally, WO 2004 / 059 079
discloses
particulate pigment compositions, useful in paper, comprising a first pigment
which is
ground calcium carbonate and a second pigment which is precipitated or ground
calcium carbonate, carbonate, the first and second pigments having different
size
distribution steepness factors (100 x d30/d70). More precisely, the claimed
particulate
pigment composition comprises two pigment components. The first comprises
particulate GCC carbonate having a steepness factor of 30-45, and the second
comprises PCC with a steepness factor of 55-75, and diameter of at most 0.5
pm, or
GCC with a steepness factor of 40-55.
First, it must be noted that neither of these two documents reveals a specific
steepness
factor of the final product, which is one of the objects of the present
invention.
Secondly, none of these documents teaches the co-grinding of GCC and PCC. It
appears clearly that these inventions are based on the mixing of both GCC and
PCC
calcium carbonate types: the skilled man encounters new problems. Finely
ground
PCC with a certain granulometry is commonly desired, said granulometry being
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achieved by grinding in dry and / or aqueous media. Nevertheless, after this
grinding
step, it has been observed that the resulting fine PCC particles collapse and
must
subsequently be de-agglomerated (processes in order to de-agglomerate such
finely
ground PCC are notably disclosed in JP 2001 089 505, JP 56 104 713, US 6 143
065 or
US 5 279 663) by mechanical means and / or by the addition of de-agglomerating
agents: this addition step represents an additional expense in the PCC
production
process ; there is a need to perform this de-agglomeration step in a cost-
efficient
manner. Finally, when co-grinding GCC and PCC as opposed to separately
grinding
each component prior to blending, in particular when using the specific ceria-
containing beads described hereafter, a surprising increase in grinding
efficiency
(decrease in total specific energy required to obtain the final products with
the desired
steepness factor) has been observed.
As indicated above, there is a need to provide the skilled man in the art
withmineral
slurries comprising both GCC and PCC for use in paper manufacturing, the
steepness
factor of the corresponding mineral being selected so that optical properties
of the
coated paper are improved, and in a cost efficient way in order to avoid,
notably, the
additional costly step of de-agglomerating PCC as necessary in the case of
simply
mixing of GCC and PCC.
Via the present invention, a new process of manufacturing a calcium carbonate
mineral
material comprising both GCC and PCC, without the drawbacks present in the
prior
art, has surprisingly been found. This process lies in a process for the
preparation of
co-ground calcium carbonate material of the GCC and PCC type, presenting a
steepness factor of at least about 30 %, preferably of at least about 40 %,
and most
preferably of at least about 45 %, comprising the step of co-grinding GCC and
PCC,
possibly with at least another mineral material.
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In some implementations, there is provided a process of manufacturing co-
ground
calcium carbonate material comprising ground calcium carbonate (GCC) and
precipitated calcium carbonate (PCC), the process comprising the steps of:
(a) providing GCC in an aqueous suspension;
(b) co-grinding the aqueous suspension of GCC and an aqueous suspension
of PCC to obtain a co-ground calcium carbonate material having a steepness
factor of at least 30;
(c) optionally screening and/or upconcentrating the co-ground calcium
carbonate material obtained following step (b); and
(d) optionally drying the co-ground calcium carbonate material obtained
following step (b) or (c);
wherein the co-grinding of GCC and PCC during step (b) is conducted in the
presence of
ceria-containing zirconium oxide grinding beads as grinding media, said beads
having:
a ceria content of between 14% and 20% by weight relative to the total weight
of
said beads; and
an average grain size after sintering of the grains forming said beads of less
than
1 pm.
The invention also provides a process of manufacturing a co-ground calcium
carbonate
material of the GCC and PCC type, presenting a steepness factor of at least
about 30,
preferably of at least about 40, and most preferably of at least 45, and
characterised in
that it comprises the steps of:
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(a) providing at least one calcium carbonate material, optionally in the form
of an
aqueous suspension,
(b) co-grinding GCC and PCC, optionally with at least another mineral
material,
(c) optionally screening and / or upconcentrating the co-ground calcium
carbonate
material obtained following step (b),
(d) optionally drying the co-ground calcium carbonate material obtained
following
step (b) or (c)
This process allows the skilled man in the art to obtain co-ground calcium
carbonate
material in the form of an aqueous suspension and / or in the form of a dry
product
comprising both GCC and PCC, which may notably be used in the paper industry.
Moreover, and due to the specific selection concerning the steepness factor of
the final
product, which must be of at least about 30, preferably of at least about 40,
and most
preferably of at least about 45, high gloss properties are achieved in the
coatedloaper.
Lastly, it has surprisingly been found that following the co-grinding step,
significant
additional PCC de-agglomeration is no longer necessary : as such, the process
according to the invention is less expensive than processes of the prior art
based on the
simple mixing of both GCC and PCC, which requires a first de-agglomeration of
PCC.
Finally, when co-grinding GCC and PCC as opposed to separately grinding each
component prior to blending, in particular when using the specific ceria-
containing
beads described hereafter, a surprising increase in grinding efficiency
(decrease in total
specific energy required to obtain the final products with the desired
steepness factor)
has been observed.
The Applicant would like also to mention EP 0 850 880, which discloses an
aqueous
slurry or dehydrated wet cake with a 25-75 % solids concentration comprising a
mixture of PCC and a viscosity reducing agent which is dispersed in a mixer to
give a
slurry with a viscosity below 1000 cp (at 25 C), and which comprises 0.2-3 gm
median diameter calcium carbonate particles. The slurry is then admixed with
1.5-30
gm median diameter dry ground calcium carbonate particles to give a weight
ratio of
to(II) of 20 : 80 to 80 : 20 and a solids concentration of 60-85 %. The slurry
is next
dispersed in a mixer to a viscosity below 1000 cp and finally dispersed in a
sand
grinding mill to give a product aqueous slurry comprising 0.2-2 gm median
diameter
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calcium carbonate particles. The EP 0 850 880 patentee teaches the above
process as a
solution to counter the high shear rheology difficulties encountered when the
GCC
component is wet ground, which is a technical problem different than the one
solved
by the present invention. By contrast, in the present invention, it has
firstly been found
that a wet grinding is also acceptable without a loss of gloss. Furthermore,
the patentee
makes no reference to any gain in production process energy via this process
that
necessitates a dry grinding of GCC. Finally, this patent does not teach that a
desirable
steepness factor can be reached for gloss improvement by an energetically
economic
process.
A first object of the invention consists in a process of manufacturing a co-
ground
calcium carbonate material comprising GCC and PCC, presenting a steepness
factor of
at least about 30, preferably of at least about 40, and most preferably of at
least about
45, and characterised in that it comprises the steps of:
(a) providing at least one calcium carbonate material, optionally in the form
of an
aqueous suspension,
(b) co-grinding GCC and PCC, optionally with at least another mineral
material,
(c) optionally screening and / or upconcentrating the co-ground calcium
carbonate
material obtained following step (b),
(d) optionally drying the co-ground calcium carbonate material obtained
following
step (b) or (c)
The process according to the invention is characterised in that in step (a),
the calcium
carbonate material is provided as an aqueous suspension, and in that this
aqueous
suspension contains from 20 % to 80 % by dry weight of calcium carbonate,
preferably
from 50 % to 75 %, and most preferably from 50 % to 70 %. Said aqueous
suspension
may result from the dispersion of calcium carbonate material in the form of a
wet cake
According to this specific embodiment, the process according to the invention
is also
characterised in that the calcium carbonate material provided in the form of
an aqueous
suspension is GCC.
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In this particular embodiment, the wet ground natural calcium carbonate may be
subjected to a wet benefication step prior to step (b), allowing the removal
of
impurities, such as silicate impurities, for instance by froth flotation.
In another embodiment, the process according to the invention is also
characterised in
that step (c) is carried out.
In another embodiment, the process according to the invention is also
characterised in
that step (d) is carried out.
More generally, the process according to the invention is also characterised
in that the
co-grinding of GCC and PCC during step (b) is conducted in aqueous medium,
wherein the concentration of calcium carbonate ranges from 20 % to 80 % (by
dry
weight of calcium carbonate), preferably from 50 % to 75 %, and most
preferably .from
50 % to 70 %.
The process according to the invention is also characterised in that at least
one
dispersing and / or grinding aid agent present in a weight % relative to the
total dry
mineral material ranging from 0 to 2 %, preferably from 0.2 % to 1.4 %, and
most
preferably from 0.5 % to 1.2 % may be added before, during or after co-
grinding in
step b).
The skilled man in the art will choose the dispersing and / or grinding aid
agent as a
function of the properties he wishes to achieve. He can use, for instance,
homopolymers of (meth)acrylic acid and / or copolymers of (meth)acrylic acid
in
combination with other water soluble monomers, such homo- and copolymers,
which
are totally or partially neutralised.
Such dispersants may be added to obtain a stable BrookfieldTM viscosity of
less than
3000 mPa.s, preferably of less than 1000 mPa.s measured at 25 C.
The process according to the invention is also characterised in that the co-
grinding of
GCC and PCC during step (b) is conducted in the presence of at least another
mineral
material selected from among talc, clay, A1203, TiO2 or mixtures thereof.
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More preferably, the other mineral material is selected among from talc, clay
or mixtures
thereof.
Most preferably, the other mineral material is talc or clay.
The process according to the invention is also characterised in that the co-
grinding of GCC
and PCC during step (b) occurs at a pH of above 7.
In another embodiment, the process according to the invention is also
characterised in that
the co-grinding of GCC and PCC during step (b) occurs at a pH of above 10.
In another embodiment, the process according to the invention is also
characterised in that
the co-grinding of GCC and PCC during step (b) occurs at a pH of above 11.
10 This pH increase can be the result of, for example, one or more of the
following: by the
addition of a base, preferably of a base of a mono or divalent cation, most
preferably of
sodium or calcium, by the addition of an alkaline preparation of a biocide, or
by the release of
hydroxide, such a Ca(OH)2, during grinding of a material, such as during the
co-grinding of
PCC and GCC. The Applicant indicates that he knows of French patent
application published
as FR 2881064, which mentions biocides that may be added during the grinding
step (b).
The process according to the invention is also characterised in that the
grinder contents are
subject to a temperature rise, to above 60 C, preferably to above 90 C, and
most preferably to
above 100 C, during step (b).
This temperature refers to the temperature reached by the mill contents at any
one point in the
mill. In particular, the mill contents at the mill base may be subject to a
higher temperature as
a result of a higher hydrostatic pressure.
The process according to the invention is also characterised in that the PCC
present
when co-grinding during step (b) accounts for 10% to 90% of the total combined
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PCC and GCC weight, preferably from 20 % to 80 % of the total combined PCC and
GCC weight, and most preferably from 30 % to 70 % of the total combined PCC
and
GCC weight.
The process according to the invention is also characterised in that the co-
grinding of
GCC and PCC during step (b), is conducted in the presence of ceria-containing
zirconium oxide grinding beads as grinding media, such beads having:
- a ceria content of between 14 % and 20 % by weight relative to the total
weight
of said bead, preferably of between 15 % and 18 % by weight relative to the
total
weight of said bead, and most preferably of approximately 16 % by weight
relative to the total weight of said bead; and
- an average gain size after sintering of the grains forming said bead , of
less
than 1 pm, preferably of less than 0.5 p.m, and most preferably of less than
0.3
This gain size is determined by analysis of scanning electron microscope
images of
the beads. Bead ceria content is analysed by ICP Optical Emission Spectrometry
The process according to the invention is also characterised in that the beads
have an
original diameter prior to grinding of between 0.2 mm and 1.5 mm, preferably
of
between 0.4 mm and 1.0 mm.
Another object of the present invention lies in the co-ground calcium
carbonate
material comprising GCC and PCC, characterised in that it is obtained by the
process
according to the invention.
Another object of the present invention lies in calcium carbonate material
comprising
GCC and PCC, characterised in that it is in the form of an aqueous suspension,
and
presents a steepness factor of at least about 30, preferably of at least about
40, and
most preferably of at least about 45.
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According to the above embodiment, the co-ground calcium carbonate material in
the
form of an aqueous suspension is also characterised in that it contains from
20 % to 80
% by dry weight of calcium carbonate material, preferably from 40 % to 75 % by
dry
weight of calcium carbonate material, and most preferably from 60 % to 70 % by
dry
weight of calcium carbonate material.
The co-ground calcium carbonate material in the form of an aqueous suspension
is also
characterised in that the PCC present accounts for 10 % to 90 % of the total
combined
PCC and GCC weight, preferably from 20 % to 80 % of the total combined PCC and
GCC weight, and most preferably from 30 % to 70 % of the total combined PCC
and
GCC weight.
The co-ground calcium carbonate material in the form of an aqueous suspension
is also
characterised in that it features a d50 from about 0.2 um to 2.0 um,
preferably, from 0.2
p.m to 0.8 p.m, and most preferably from 0.25 p.m to 0.45 um. This cis() is
measured
using a SedigraphTM 5100.
The co-ground calcium carbonate material in the form of an aqueous suspension
is also
characterised in that the aqueous suspension contains at least one dispersing
and / or
grinding aid agent, such dispersing and / or grinding aid agent being present
in a
weight % relative to the total dry mineral material ranging from 0 to 2 %,
preferably
from 0.2 % to 1.4 %, most preferably from 0.5 % to 1.2 %.
The co-ground calcium carbonate material in the form of an aqueous suspension
is also
characterised in that the slurry water passed through a 40 p.m sieve contains
less than
1000 ppm of Zr02 and less than 200 ppm Ce02. Zr02 and Ce02 contents are
determined by ICP-OES.
The co-ground calcium carbonate material in the form of an aqueous suspension
is also
characterised in that the slurry water features a Zr02/Ce02 weight ratio of
from 4 to
6.5, preferably of from 4.6 to 5.7, and most preferably of 5.3.
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The co-ground calcium carbonate material in the form of an aqueous suspension
is also
characterised in that it contains:
- a fraction of particles finer than 1 pm of greater than 80 %,
preferably of
greater than 85 %, more preferably of greater than 90 %, and even more
preferably of greater than 95 %, and
- a BET specific surface area of less than 25 m2/g.
When the fraction of particles finer than 1 tm is greater than 95 %, the BET
specific
surface area is preferably less than 25 m2/g. When the fraction of particles
finer than 1
p.m is greater than 90 %, greater than 85 %, and greater than 80 %, the BET
specific
surface area is preferably less than 20 m2/g, less than 18 m2/g, and less than
15 m2/g,
respectively.
Another object of the present invention lies in the co-.ground calcium
carbonate
material comprising GCC and PCC, characterised in that it is in the form of a
dry
product, presenting a steepness factor of at least about 30, preferably of at
least about
40, and most preferably of at least about 45.
The co-ground calcium carbonate material in the form of a dry product is also
characterised in that the PCC present accounts for 10 % to 90 % of the total
combined
PCC and GCC weight, preferably from 20 % to 80 % of the total combined PCC and
GCC weight, and most preferably from 30 % to 70 % of the total combined PCC
and
GCC weight.
The co-ground calcium carbonate material in the form of a dry product is also
characterised in that it contains:
- a fraction of particles finer than 1 p.m of greater than 80 %,
preferably of
greater than 85 %, more preferably of greater than 90 %, and even more
preferably of greater than 95 %, and
- a BET specific surface area of less than 25 m2/g.
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When the fraction of particles finer than 1 gm is greater than 95 %, the BET
specific
surface area is preferably less than 25 m2/g. When the fraction of particles
finer than 1
1.1.M is greater than 90 %, greater than 85 %, and greater than 80 %, the BET
specific
surface area is preferably less than 20 m2/g, less than 18 m2/g, and less than
15 m2/g,
respectively.
The co-ground calcium carbonate material in the form of a dry product is also
characterised in that it features a d50 from about 0.2 gm to 2.0 gm,
preferably from 0.2
um to 0.8 gm, and most preferably from 0.25 gm to 0.45 pm. This (150 is
measured
using a SedigraphTM 5100.
The co-ground calcium carbonate material in the form of a dry product is also
characterised in that it features a Zr02/Ce02 weight ratio of from 4 to 6.5,
preferably of
from 4.6 to 5.7, and most preferably of 5.3.
Finally, another object of the present invention lies in the use of the co-
ground calcium
carbonate material according to the invention, in any sector making use of
mineral
material, and notably in the paper, paint and plastic industries.
WO 2007/031870 CA 02880965 2015-02-03 PCT/1B2006/002655
EXAMPLES
The following examples are intended to illustrate certain embodiments of the
invention
and are non-limitative.
5
Median diameter (d5o) and the fraction of particles featuring a diameter below
a given
diameter value were measured using a SedigraphTM 5100.
Example 1 ¨ Comparative Example
Ground calcium carbonate presenting a median diameter of 1.5 gm was wet-ground
at
a solids content of 74.5 % in the presence of the following additives: 1.51 %
sodium
polyacrylate, in a two-pass process using ceria-comprising zirconium oxide
grinding
beads featuring a median bead diameter of 0.45 mm, a Ce02 content of r6;:% by
weight relative to the total bead weight, and a grain size after sintering of
0.4 um
(determined by evaluations of SEM images). The specific grinding energy
required to
obtain a final GCC with a steepness factor of about 35 % was of 270 kWh/t.
The obtained slurry of the ground GCC material featuring a subsequently
diluted solids
content of 75 % was then added to a standard paper coating formulation made up
of
the following proportions of components:
100 parts ground GCC material
10.5 parts SBR latex
0.5 parts synthetic thickener
0.2 parts polyvinyl alcohol
0.2 parts optical brightening agent
The above coating was adjusted to a final solids content of 68 % and applied
on a
standard pre-coated wood-free base paper with a grammage of 71 g/m2 at a coat
weight
of 10 g/m2/side. This coated base paper was then calendered using a
supercalender
under the following calendering conditions: calender speed of 800 m/min,
calender
load of 200 kN/cm and a temperature of 105 C.
WO 2007/031870 CA 02880965 2015-02-03 PCT/1B2006/002655
16
The gloss of the coated paper surface was of 70 % Tappi 75 .
Example 2 ¨ Illustration of the process according to the invention
A 76 % solids content slurry of ground calcium carbonate presenting a median
GCC
diameter of 1.4 p.m was ground in the presence of a 51 % solids content PCC
slurry
with a median PCC diameter of 0.75 p.m. The PCC to GCC weight ratio in the
mill
was of 50:50. The total solids content of the slurry in the mill was of 61 %
and a
median diameter of 1.1. The grinder contents were then co-ground in the
presence of
the following total additives content: 0.95 weight % sodium polyacrylate,
using ceria-
comprising zirconium oxide grinding beads featuring a median bead diameter of
0.45
mm, a Ce02 content of 16 % by weight relative to the total bead weight, and
a.grain
size after sintering of 0.4 p.m (determined by evaluations of SEM images). The
specific
grinding energy required to obtain a final co-ground product with a steepness
factor of
about % 42 was of 200 kWhit.
The obtained slurry of the co-processed material featuring a solids content of
70.2 %
was then added to a standard paper coating formulation made up of the
following
weight proportions of components:
100 parts co-processed material
10.5 parts SBR latex
0.5 parts synthetic thickener
0.2 parts polyvinyl alcohol
0.2 parts optical brightening agent
The above coating was adjusted to a final solids content of 68 % and applied
on a
standard pre-coated wood-free base paper with a grammage of 71 g/m2 at a coat
weight
of 10 g/m2/side. This coated base paper was then calendered using a
supercalender
under the following calendering conditions: calender speed of 800 m/min,
calender
load of 200 kN/cm and a temperature of 105 C.
WO 20()7/031870 CA 02880965 2015-02-03 PCT/1B2006/002655
17
The gloss of the coated paper surface was of 72 % Tappi 75 .
The above results are summarised in Table 1.
Table 1:
Example 1 Example 2
Fraction of particles finer than 1 97 % 97 %
P.M in the final ground product
BET specific surface area of the 28 g/m2 23 g/m2
final ground product
Steepness factor of the final 35 42
ground product
Median diameter of the final 0.271= 0.27
ground product
Total specific grinding energy 270 kWhit 200 kWh/t
required to produce the product
Tappi gloss of paper coated with 70 % 72 %
a formulation comprising the
product
Brightness of paper coated with 95.1 % 96.5 %
a formulation comprising the
product
Opacity of paper coated with a 89.7 % 90.2 %
formulation comprising the
product
Table 1 illustrates that the process according to the invention requires less
specific
grinding energy, and leads to an equal/improved gloss, relative to a process
of the prior
art.
Example 3 ¨ Comparative example
This example illustrates a blend of PCC and GCC, in which each component is
first
separately ground prior to being mixed.
A 48 % solids aqueous slurry of PCC starting material having the
characteristics
indicated under Example 3 in Table 2 was ground in a media mill using yttrium-
stabilised zirconium silicate grinding beads featuring a bead diameter prior
to grinding
of 0.6 to 1.0 mm. A total of 50 kWhit specific grinding energy was expended in
order
to obtain a PCC end material having the end material characteristics indicated
in Table
WO 2007/03187() CA 02880965 2015-02-03 PCT/1B2006/002655
18
2. The final solids content of this subsequently upconcentrated PCC slurry was
of 68
%.
Separately, a 74 % solids aqueous slurry of GCC starting material having the
characteristics indicated under Example 3 in Table 2 was ground in a media
mill using
yttrium-stabilised zirconium silicate grinding beads featuring a bead diameter
prior to
grinding of 0.6 to 1.0 mm. A total of 210 kWhit specific grinding energy was
expended in order to obtain a GCC end material having the end material
characteristics
indicated in Table 2. The final solids content of this GCC slurry was of 75 %.
The PCC and GCC slurries were then mixed so as to obtain a PCC/GCC blend
material with a PCC:GCC weight ratio of 30:70. This slurry was then added to a
standard paper coating formulation made up of the following weight proportions
of
components:
100 parts PCC/GCC blend material
10.5 parts SBR latex
0.5 parts synthetic thickener
0.2 parts polyvinyl alcohol
0.2 parts optical brightening agent
The above coating was adjusted to a final solids content of 68 % and applied
on a
standard pre-coated wood-free base paper with a grammage of 71 g/m2 at a coat
weight
of 10 g/m2/side. This coated base paper was then calendered using a
supercalender
under the following calendering conditions: calender speed of 800 m/min,
calender
load of 2001(1\1/cm and a temperature of 105 C.
The optical properties of the coated paper surface are given in Table 2.
Example 4 ¨ Example according to the invention.
This example illustrates a co-ground PCC and GCC obtained by a process
according to
the invention.
WO 2007/031870 CA 02880965 2015-02-03 PCT/1B2006/002655
19
A 74 % solids content slurry of ground calcium carbonate presenting the
characteristics listed under Example 4 in Table 2 was ground in the presence
of a 48 %
solids content PCC slurry with the characteristics listed under Example 4 in
Table 2 in
a media mill. The PCC to GCC weight ratio in the mill was of 30:70 and the
solids
content of 65.9 %. The grinder contents were co-ground using yttrium-
stabilised
zirconium silicate grinding beads featuring a bead diameter prior to grinding
of 0.6 to
1.0 mm. A total of 116 k'Whit specific grinding energy was expended in order
to obtain
a GCC/PCC co-ground end material having the end material characteristics
indicated
in Table 2. The final solids content of this GCC slurry was of 70.3 %.
This slurry was then added to a standard paper coating formulation made up of
the
following weight proportions of components:
100 parts PCC/GCC co-ground material
10.5 parts SBR latex
0.5 parts synthetic thickener
0.2 parts polyvinyl alcohol
0.2 parts optical brightening agent
The above coating was adjusted to a final solids content of 68 % and applied
on a
standard pre-coated wood-free base paper with a grammage of 71 g/m2 at a coat
weight
of 10 g/m2/side. This coated base paper was then calendered using a
supercalender
under the following calendering conditions: calender speed of 800 m/min,
calender
load of 200 kN/cm and a temperature of 105 C.
The optical properties of the coated paper surface are given in Table 2.
WO 2007/031870 CA 02880965 2015-02-03 PCT/1B2006/002655
Table 2:
Product Name Example 3: PCC/GCC Example 4:
Blend Material PCC/GCC Co-
Ground
Material
Starting material characteristics
GCC dso (I-Lm) 1.4 1.4
Steepness factor 28 28
PCC clso (lim) 0.75 0.75
Steepness factor 55 55
End material characteristics
GCC d50 (1-tm) 0.40
Steepness factor 34
PCC dso (Inn) 0.38 --
Steepness factor 40
PCC / GCC PCC/GCC weight ratio 30/70 30/70
d50 (Full) 0.38 0.40
Steepness factor 37 38
Fraction of particles 89.5 88.8
with a diameter less
than 2 p.m (%)
BET specific surface 18.1 18.2
area (g/m2)
Total specific grinding energy 162 kWh/t 116 kWh/t
Characteristics of paper coated with the end material
Paper gloss (Tappi 75 ) 70.5 % 72 %
Opacity 90.4 % 90.5 %
Brightness R457 97.9 % 97.9 %
= 5 Table 2 indicates that the process to prepare a co-ground PCC/GCC
material according
to the invention requires less grinding energy as compared to that required to
prepare a
comparable blend of PCC and GCC, without any loss or with an improvement in
optical properties.
Example 5
This example illustrates the use of a process according to the invention
wherein 3
minerals, a natural calcium carbonate a precipitated calcium carbonate and a
clay, are
co-ground with the use of ceria-containing zirconium oxide grinding beads with
a ceria
content of 16 % by weight relative to the total weight of said bead, an
average grain
size after sintering of the grains forming said bead of 0.4 pm , and a median
bead
diameter of 0,45 mm. The co-ground material is then added to a coating
formulation
used to coat a base paper, and the resulting gloss is measured.
= WO 2007/031870 CA 02880965
2015-02-03 PCT/1B2006/002655
21
The following materials were co-ground:
- a 74 % solids content slurry of ground calcium carbonate presenting a
median
GCC diameter of 1.4 gm and prepared using 0.27 % weight (by weight of dry
GCC) of an homopolymer of acrylic acid,
- a 51 %
solids content PCC slurry with a median PCC diameter of 0.8 pm and
prepared using 0.7 % weight (by dry weight of PCC) of an homopolymer of
acrylic acid,
- and a 68 % solids content slurry of clay commercialized by HUBERTm
under
the name LithoprintTM.
The weight ratio PCC:GCC:clay in the mill was of 45:45:10.
The total solids content of the slurry in the mill was of 72 c/o and the
median diameter
was of 0.4 and 0.5 pm for the 2 tests illustrating the invention.
The grinder contents were then co-ground in the presence of the following
total
additives content:
- respectively 0.4 and 0.2 weight % (by dry weight of mineral matter)
of an
homopolymer of acrylic acid, where 14 mol % of the carboxylic functions are
neutralized by sodium hydroxyde, having a molecular weight of 5 600 g/mol,
and a polydispersity equal to 2.4,
- using ceria-comprising zirconium oxide grinding beads featuring a median
bead diameter of 0.45 mm, a Ce02 content of 16 % by weight relative to the
total bead weight, and a grain size after sintering of 0.45 gm,
leading to a coground material exhibiting a median diameter respectively of
0.4 and
0.5 um.
The 2 obtained slurry of the co-processed material was then added to a
standard paper
coating formulation made up of the following weight proportions of components:
100 parts co-processed material
11 parts SBR latex (DL 966 commercialized by DOW
CHEMICALSTm)
0.5 parts synthetic thickener (CMC FF5 commercialized by
FINNFJXTM)
WO 2007/()31870 CA 02880965 2015-02-03
PCT/IB2006/002655
22
0.4 parts polyvinyl alcohol (PVA 4-98 commercialized by
CLARIANTTm)
0.6 parts optical brightening agent (BlancophorTM P commercialized
by
BAYERTM)
The above coating was applied on a standard topcoat base paper with a grammage
of
78 g/m2 at a coat weight of' 10 g/m2/side. This coated base paper was then
calendered
using a supercalender under the following calendering conditions: calender
speed of
300 m/min, calender load of 170 kN/m and a temperature of 80 C.
For the coground material exhibiting a median diameter of 0.4 pm, the gloss of
the
coated paper surface was 0f73 % Tappi 75 and 45 % DIN 75 .
By comparison, the same coating manufactured with 100 parts of a GCC having a
median diameter of 0.4 pm was of 70 % Tappi 75 and 35 % DIN 75 .
For the coground material exhibiting a median diameter of 0.5 pm, the gloss of
the
coated paper surface was of 68 % Tappi 75 and 40 % DIN 75 .
By comparison, the same coating manufactured with 100 parts of a GCC having a
median diameter of 0.4 pm was of 63 % Tappi 75 and 33 % DIN 75 .
